Inorganic coating and composition

ABSTRACT

This disclosure relates to basic inorganic compositions. Methods of providing antifungal/antibacterial resistance and/or hydrophobicity and/or corrosion resistance by coating surfaces with the basic inorganic compositions are provided. In another aspect, a silicate composition comprising at least one alkali earth metal; and a Group IV element of silicon, germanium, tin, or lead having at least one hydrocarbon moiety covalently bonded thereto is provided.

TECHNICAL FIELD

This disclosure relates to inorganic coatings, specifically, thecomposition, manufacture, and method of providing resistance to moldand/or bacterial growth and/or waterproofing and/or corrosion protectionto corrodible metal surfaces. The composition comprises at least onesparingly soluble basic metal oxide or metal hydroxide, one or moresparingly soluble inorganic silicates, and a basic inorganic salt.

BACKGROUND

Providing bacterial and/or mold resistance to metallic and non-metallicsurfaces, without the use of fungicidal and bactericidal chemicals inthe form of coatings has proven elusive. Typically, one or morefungicides and bactericides are included in the pre-set formulation inthe desire to have them bloom or migrate to the surface upon or aftersetting. Such techniques result in the dissipation of thefungicidal/bactericidal properties over time and further require usingan excess of such additives. Moreover, the use of specific fungicidesand bactericides or classes of fungicides and bactericides ultimatelyresults in resistant strains of these organisms. Providing waterproofingto inorganic coatings has also proven elusive. Providing bothwaterproofing and bacterial and/or mold resistance coatings has proveneven more elusive.

Otherwise basic substances and surfaces, or media of high pH is at leastpartially effective for measurable control of certain microbes.“Water-glass” or soluble silicates, for example, sodium or potassiumsilicate, and/or the sodium or potassium salt of silicic acid salt, ordisodium metasilicate, which can be basic depending on SiO2:Na2O ratios,are sometimes used as an anti-microbial surface treatment whenformulated as a silicate mineral paint having the water glass as abinder. However, such silicate mineral paints are typically prepared ascoating formulations using a weak acid, e.g., carbonate salt (forstability), thus rendering the solution and the subsequent coating to apH of less than 9, and they need a fixative to seal the silicate to thesubstrate.

SUMMARY

In a first embodiment, a composition is provided. The compositioncomprising: at least one aqueous sparingly soluble metaloxide/hydroxide; at least one sparingly soluble inorganic mineral; andat least one soluble basic inorganic salt.

In one aspect, the at least one sparingly soluble metal oxide/hydroxideis at least one of magnesium oxide, magnesium hydroxide, calcium oxide,and calcium hydroxide. In other aspects, the at least one sparinglysoluble metal oxide/hydroxide is at least one of barium oxide, zincoxide, copper oxide, and hydroxides thereof.

In one aspect, alone or in combination with any of the previous aspects,the at least one sparingly soluble inorganic mineral is one or more ofan inorganic mineral silicate, wollastonite, talc, amorphous magnesiumsilicate, amorphous calcium silicate, diatomaceous earth,aluminosilicate, olivine, calcined kaolin, mullite, colloidal silica,silicon dioxide, and amorphous silicon dioxide.

In one aspect, alone or in combination with any of the previous aspects,the at least one soluble basic inorganic salt is one or more of analkali metal or alkali earth metal salt of one of a phosphate, or asilicate. In one aspect, alone or in combination with any of theprevious aspects, the at least one soluble basic inorganic salt is oneor more of an alkali metal or alkali earth metal hydroxide.

In one aspect, alone or in combination with any of the previous aspects,the composition further comprises at least one hydrophobic agent,wherein the hydrophobic agent is of the general formula (I) or (II) or(III) or (IV):

where:

R₁, R₂, R₃, and R₄ are, independently, hydrogen, C₁₋₂₀ alkyl, phenyl,aryl; where alkyl includes straight-chain, branched, cyclic or acylicalkyl, or haloalkyl;

Y₁, Y₂, and Y₃ is, independently, hydroxyl, C₁₋₄ alkoxy, phenoxide, orhalogen; or, Y₁, Y₂, and Y₃ is, independently, an alkali metal salt, anammonium salt, an alkylammonium salt, a phenylammonium salt, or analklyphenylammonium salt of Si—OH;

b is 0-21; n is greater than 1,000 to 1,000,000;

m is 0-1,000; and

Z is sodium or potassium.

In one aspect, alone or in combination with any of the previous aspects,the organosiliconate is a potassium salt, e.g., a mono-, di-, ortri-alkyl siliconate.

In a second embodiment, method of preventing or reducing fungal orbacterial growth on a surface is provided. The method comprising:combining the composition of the first embodiment; contacting a surfacewith the combined composition, wherein the surface, after contacting,provides a basic environment of at least pH 9 to pH 14; and reducing oreliminating fungal or bacterial growth on the surface.

In one aspect, alone or in combination with any of the previous aspects,the surface is metal or non-metal. In one aspect, the surface isassociated with a medical article, medical device, or structure.

In one aspect, alone or in combination with any of the previous aspects,the combining is performed with high shear.

In one aspect, alone or in combination with any of the previous aspects,the contacting is at least one of painting, brushing, troweling, andspraying.

In a third embodiment, method of preventing or reducing fungal orbacterial growth on a surface is provided. The method comprising:combining the precursor formulation of any of the previous embodimentsor aspects; contacting a surface with the combined precursor formulationof any of the previous embodiments or aspects, wherein the surface,after contacting, provides a basic environment of at least pH 9 to pH14; and preventing or reducing fungal or bacterial growth on thesurface.

In one aspect, alone or in combination with any of the previous aspects,the at least one sparingly soluble metal oxide/hydroxide component isone or more of magnesium oxide, magnesium hydroxide, magnesium brinecontaining an effective amount of magnesium hydroxide, calcium oxide,and calcium hydroxide. In one aspect, the at least one sparingly solublemetal oxide/hydroxide component is at least one of barium oxide, zincoxide, copper oxide, and hydroxides thereof.

In one aspect, alone or in combination with any of the previous aspects,the at least one soluble basic inorganic salt is one or more of analkali metal or alkali earth metal salt of one of a phosphate, asilicate, or an alkylsiliconate. In one aspect, the at least one solublebasic inorganic salt is an organosiliconate or potassium salt of anorganosiliconate. The at least one organosiliconate can be a mono-, di-,or tri-alkyl silicate. In one aspect, the at least one soluble basicinorganic salt is an alkali hydroxide or alkali earth hydroxide.

In one aspect, alone or in combination with any of the previous aspects,wherein the at least one soluble basic inorganic salt is potassiumphosphate (K₂PO₄).

In one aspect, alone or in combination with any of the previous aspects,the hydrophobic agent is as described above for the first embodiment.

In one aspect, alone or in combination with any of the previous aspects,the at least one sparingly soluble inorganic mineral is one or more ofwollastonite, talc, amorphous magnesium silicate, amorphous calciumsilicate, diatomaceous earth, aluminosilicate, olivine, calcined kaolin,mullite, colloidal silica, silicon dioxide, and amorphous silicondioxide.

In a fourth embodiment, method of preventing or reducing corrosion of acorrodible surface is provided. The method comprising: contacting acorrodible surface with the combined composition alone or in combinationwith any of the previous aspects thereof; and preventing or reducingcorrosion on the corrodible surface.

In a fifth embodiment, a method of preventing or reducing attachment ofMollusca on a surface is provided. The method comprising: contacting asurface with the combined composition alone or in combination with anyof the previous aspects thereof, wherein the surface, after contacting,provides a basic environment of at least pH 9; and preventing orreducing attachment of Mollusca on the surface. In one aspect, theMollusca are fresh water mussels. In other aspect, the Mollusca arezebra mussel or quagga mussel.

In a sixth embodiment, a silicate composition is provided. The silicatecomposition comprising at least one alkali earth metal and at least oneGroup IV element of silicon, germanium, tin, or lead having at least onehydrocarbon moiety covalently bonded thereto. In a first aspect, the oneor more hydrocarbon moiety is independently, C₁₋₂₀ alkyl, phenyl, aryl;where alkyl includes straight-chain, branched, or cyclic alkyl,haloalkyl (e.g. fluoro- or chloro alkyl). In one aspect, the at leastone alkali earth metal is magnesium or calcium. In another aspect, aloneor in combination with any of the previous aspects, the at least oneGroup IV element is silicon. In another aspect, alone or in combinationwith any of the previous aspects, the alkyl group is methyl, ethyl,butyl, sec-butyl, or t-butyl. In another aspect, alone or in combinationwith any of the previous aspects, the at least one alkali earth metal ismagnesium and the at least one Group IV element is silicon, and thehydrocarbon is methyl.

BRIEF DESCRIPTION OF THE DRAWINGS

NONE

DETAILED DESCRIPTION

The present disclosure provides uniquely-suited, inorganic coatingshaving, among other things, hydrophobic properties that minimize orreduce the penetration of water and/or corrosion of metals, for examplesteels and iron and make it unnecessary to use alloys of steel or ironsuch as galvanized (zinc coated) compositions or chrome platedcompositions.

In addition, the present disclosure provides inorganic coatingsproviding management of fungal/bacterial growth resistance.

As used herein phrases “sparingly soluble basic metal oxide andsparingly soluble basic metal hydroxide component” and “sparinglysoluble basic component” and “sparingly soluble alkaline component” and“sparingly soluble alkaline precursor” are used interchangeably unlessotherwise indicated. The phrases “sparingly soluble basic component” and“sparingly soluble alkaline component” and “sparingly soluble alkalineprecursor” arc inclusive of materials that are sparingly soluble, e.g.,have low solubility product constants in aqueous media, e.g., e.g.,solubility constants (Ksp) of at least 10⁻⁴, 10⁻⁵, 10⁻⁶, 10⁻⁷, 10⁻⁸,10⁻⁹ or smaller. In one aspect, the solubility of the sparingly solublebasic component is less than about 0.1 moles/liter water. In one aspect,the phrases sparingly soluble basic metal oxide and sparingly solublebasic metal hydroxide component” and “sparingly soluble basic component”and “sparingly soluble alkaline component” and “sparingly solublealkaline precursor” are exclusive of materials that are readily soluble,e.g., have high solubility product constants in aqueous media.

As used herein, the phrase “soluble basic inorganic salt” is inclusiveof materials that are readily aqueous soluble, e.g., solubilityconstants (Ksp) of at least 10⁻³, 10⁻² or greater, and have an aqueouspH of between about 10 to about 14, between about 11 to 14, betweenabout 12 to 14, or between about 13 to 14. In one aspect, the solubilityof the soluble basic inorganic salt is greater than about 0.1moles/liter water, or greater than about 1 moles/liter water. “Basicinorganic salt of an inorganic acid” and “basic inorganic salt” include,by way of example, one or more of a bi-, and/or tri-alkali and/or alkaliearth salt of phosphate (PO₄ ³), silicate (SiO₄ ⁻³), alkyl silicate(alkyl-SiO₃ ⁻³), or aluminate (Al₂O₄ ⁻²). Other readily aqueous solublebasic inorganic salts, providing an aqueous pH of greater than 10,greater than 11, greater than 12, greater than 13, or an aqueous pH ofbetween 10 and 14, can be used, for example, potassium hydroxide, and toa lesser extent, sodium hydroxide. The amount of basic inorganic saltpresent in an aqueous mixture of the sparingly soluble basic metaloxide/hydroxide component, alone or in combination with one or moresparingly aqueous soluble inorganic silicates, can be between about 1weight percent to about 95 weight percent, or about 3-75 weight percent,or 5-50 weight percent solids.

As used herein, the phrase “aqueous mixture” refers to a combination ofat least a quantity of water and at least one of the sparingly solublebasic component. For example, the aqueous mixture can contain mostlywater and suspended, dispersed, or slurried components, and may alsocontain non-aqueous components such as alcohols and other solvents.Preferably, water is the major liquid phase. The amount of basicinorganic salt present in the aqueous mixture of the sparingly solublebasic metal oxide/hydroxide component, alone or in combination with oneor more sparingly aqueous soluble inorganic silicates, can be betweenabout 1 weight percent to about 75 weight percent, or about 2-50 weightpercent, or 3-20 weight percent solids.

The amount of total solids (e.g., basic component and/or other solids)present in the aqueous mixture can be between 10 weight percent to about95 weight percent, 35-90 weight percent, or 50-80 weight percent solids.

Examples of the basic inorganic coatings provided herein include asparingly aqueous soluble metal oxide/hydroxide and sparingly aqueoussoluble inorganic silicate with an aqueous soluble basic inorganic salt.Another example of the basic inorganic coatings provided herein includethe combination of one or more metal oxide/hydroxide, one or moresparingly aqueous soluble inorganic mineral, e.g., a silicate, with oneor more aqueous soluble basic inorganic salt.

In one example of the coatings disclosed herein, one or more metaloxide/hydroxide such as magnesium oxide/hydroxide and/or calciumoxide/hydroxide is combined with one or more sparingly soluble inorganicminerals, such as wollastonitc, talc, amorphous magnesium silicate,amorphous calcium silicate, diatomaceous earth, silicon dioxide,calcined kaolin, colloidal silica, and amorphous silicon dioxide, andone or more of an aqueous soluble basic inorganic salt is added toprovide stability to the mixture. In one aspect, the aqueous solublebasic inorganic salt comprises one or more of an alkali or alkali earthsalt of a phosphate, a silicate, or an alkyl-, or aryl-siliconate. To beclear, the aqueous soluble basic inorganic salt of a silicate or analkyl-, aryl-siliconate are not simply “fillers.” The introduction ofthe alkyl-, aryl-siliconatc salt provides for an inorganic-organicsilicate composition with unique properties, namely, improvedhydrophobicity, improved corrosion resistance, and improved microbialresistance. The inorganic-organic silicate composition can be appliedfrom a precursor formulation as a coating to a substrate, or used as amonolithic form such as a floor, wall, or other architectural component.

These compositions are disclosed herein for providing coatings onsteels, aluminum, and other metal or non-metal surfaces to reduce oreliminate fungal and/or bacterial growth thereon as well as providehydrophobicity and/or corrosion protection. Additional agents can beadded to the above, such as hydrolysable silicones, polysilicones, andcombinations thereof, to impart additional properties to the coating,such as improved water resistance. The amount of the additionaladditives is such that the basic property of the coating is maintained,yet the water resistance is improved. Such loadings of additionaladditives can be about 1 to about 20 weight percent. In one aspect, thealkylsiliconate salt can be both the soluble basic inorganic salt andthe hydrophobic agent.

In another example of the coatings disclosed herein, one or more metaloxide/hydroxide such as magnesium oxide/hydroxide and/or calciumoxide/hydroxide is combined with one or more sparingly soluble inorganicminerals, such as wollastonite, talc, amorphous magnesium silicate,amorphous calcium silicate, diatomaceous earth, silicon dioxide,calcined kaolin, colloidal silica, and amorphous silicon dioxide, andone or more of an aqueous soluble basic inorganic salt is added to forma precursor formulation. These compositions are disclosed herein forproviding coatings on steels, aluminum, and other metal or non-metalsurfaces to provide hydrophobicity, and/or reduce or eliminate fungaland/or bacterial growth thereon.

In one aspect, the present coatings provide an environment that isbasic, for example, having a pH greater than what is biologicallyincompatible with the growth and/or colonization of bacteria and/orfungus (or mold). The pH of the environment can be adjusted to begreater than pH 9 to pH 14, between pH 9.5 and 14, between pH 10 and13.5, or pH 10 to about 13. The environment of the coating includes thesurface and the bulk thereof. The environment can be realized underambient conditions of typical relative humidity or humid conditions.Such environments are effective in reducing or eliminating microbialgrowth and effective in at least partially neutralizing or killing oneor more microbes that are presented to the surface of the coating.

In addition to reducing or eliminating fungal and/or bacterial growth,the coatings herein disclosed can be essentially water repellant and/orwater impermeable. For example, a magnesium potassium phosphate and/orcalcium potassium phosphate, calcium silicate (wollastonite) and/ormagnesium silicate, and one or more alkylsilicates, such as potassiummethylsiliconate, sodium methylsiliconate, potassium ethylsiliconate, orsodium ethylsiliconate, and the like can be used to provide ahydrophobic inorganic coating.

The above basic inorganic compositions can be used as monolithic forms,or as coatings that serve as a surface treatment for a metal ornon-metal, a function it performs effectively with excellent adhesionand typically without primer layers. In contrast to the conventionalmethods of including chemicals for providing the fungal/bacterialresistance, the present coatings, in part due to the basic nature of thematerial, provides an environment that is toxic or otherwiseincompatible with the growth and/or colonization of bacteria and/orfungus (or mold).

Stabilizing Metal Oxide/Hydroxide and Inorganic Mineral Compositions

The aqueous suspension of sparingly soluble basic component useful forcoatings preferably comprises sparingly soluble alkali minerals such asone or more inorganic mineral silicates, wollastonite, amorphousmagnesium silicate, amorphous calcium silicate, amorphous silica,soluble glass, diatomaceous earth, olivine, and the like. These mixturesarc generally unstable when combined in aqueous media, tending torapidly congeal or increase in viscosity in a short period of time. Ithas now been found, that one or more of a readily aqueous soluble basicalkali or alkali earth salt of a phosphate, a silicate, or analkylsiliconate (or arylsiliconate) can effective stabilize thesparingly soluble basic metal oxide and sparingly soluble inorganicmineral composition. It has also been observed that aqueous solublebasic alkali or alkali earth hydroxides can be used, however, potassiumhydroxide appears superior in performance to that of sodium hydroxide atequivalent loading. While not to be held to any particular theory, it isbelieved that potassium cation and/or phosphate anion contributes, inpart, to the stabilization of the basic metal oxide/hydroxide andmineral silicate mixture. By providing to the above sparingly solublebasic metal oxide and sparingly soluble inorganic mineral coatingcomposition a readily aqueous soluble basic alkali or alkali earth salt,for example, a potassium salt, a phosphate, a silicate, or analkylsiliconate, said readily aqueous soluble basic alkali or alkaliearth salt of a phosphate, a silicate, or an alkylsiliconatc having anaqueous pH between about 9 to about 14, more preferably a pH betweenabout 10 to about 13, effective stabilization is provided, and a stable,useful coating or precursor composition is obtained. The abovestabilized metal oxide/hydroxide, inorganic mineral, and soluble basicinorganic salt composition can be used as a coating for surfaces toprevent or eliminate fungal and/or bacterial growth. In one aspect, theamount of readily aqueous soluble basic alkali or alkali earth salt of aphosphate, a silicate, or an alkylsiliconate needed to stabilize thesparingly soluble basic metal oxide and sparingly soluble inorganicmineral composition is about 1 weight percent to about 30 weightpercent, or about 2 weight percent to about 20 weight percent, or about3 weight percent to about 10 weight percent, depending on the loading ofoxide and mineral.

In one aspect, the surface of an article can be provided with a basicnature using the coating provide herein, for example, the coating canprovide a basic environment of between about pH 9 and about pH 15,between about pH 9.5 and about pH 13, between about pH 10.0 and about pH12, and between about pH 10 and about pH 11. Such basic environmentsprevent or inhibit fungal, bacterial and/or microorganism growth orcolonization on the surface of the coated article and/or kill orneutralize subsequent contamination of the coated article by suchmicrobes. The coated article can be, for example, a medical articleand/or device and/or equipment and/or component, as well as a floorand/or wall surface. After application of the coating composition to asurface or substrate, it “sets” or “sets-up” to a glass-like coatingthat is securely bonded to the surface or substrate. After set, thecoating is resistant to removal by washing, scraping, or duringcleaning.

The final pH of the set coating herein disclosed is in the passivationrange of steel, e.g., between about pH 9 and about pH 13, between aboutpH 9.5 and about pH 11.5, between about pH 10.0 and about pH 11.0,between about pH 9.0 and about pH 10.5, between about pH 9.5 and aboutpH 10.0, between about pH 10.0 and about pH 10.5. Therefore, the coatingcan offer corrosion protection as well as fungal, bacterial and/ormicroorganism inhibition, and can further provide hydrophobicity.

In one embodiment, one or more known antifungal and/or antibacterialagents can be included in the composition, provided that the efficacy ofthe agent is not affected by the basic nature of the composition before,during, or after coating of a substrate. In one aspect, however, noantifungal and/or antibacterial agents are used, the coating having asurface pH effective to prevent or eliminate fungal and/or bacterialgrowth.

In one aspect, a method of preventing or reducing attachment of Molluscaon a surface is provided. Thus, a surface, for example, a portion or theentirety of a water treatment facility, such as water intake tubes orconduits, can be coated with a coating comprising the precursorformulation of any of the previous embodiments or aspects above, so asto provide the surface, after contacting, a basic environment of atleast pH 9, at least pH 9.5, at least pH 10. The surface having a highpH prevents or reduces Mollusca attachment, as most Mollusca prefer anenvironment having a pH of about 7.2 to 9. While not to be held to anyparticular theory, it is believed that the high pH surface of theinstant coating at least interferes with byssal thread attachment to thebasic surface and/or weakens the byssus, and/or is a toxic environmentfor the Mollusca and/or their larvae or veliger. In one aspect, theMollusca are fresh water mussels. In one aspect, the Mollusca are zebramussels or quagga mussels. The present basic coatings provide analternative to toxic copper, zinc, or tin coatings.

In one aspect, the instant compositions can be configured as anatomizible, sprayable, inorganic composition. The inorganic compositionscan be sprayed at a relatively thin thickness. The compositions can holdhigh solids contents and yet still hold the solids until setting andthus avoiding the solids migrating or dislodging from the point ofapplication, e.g., down a wall, beam, curved surface, or from a ceilingsurface. Such spray coated compositions produce high-strength,rapid-setting coatings that provide fungal/bacterial protection suitablefor spray coating on metal or non-metal surfaces, for example, medicaldevices, equipment, components, and the like.

In one aspect, the atomizable composition can comprise an aqueoussolution, suspension, or slurry comprising a sparingly aqueous solublealkaline oxide or alkaline hydroxide represented by B_(2m)O_(m),B(OH)_(2m), or mixtures thereof, where B is an element of valency 2m(m=1, 1.5, or 2); a sparingly aqueous soluble inorganic silicate, and asoluble basic inorganic salt, adjusted to a pH of between 9-15, andoptionally a rheology modifier/suspending agent in an amount capable ofproviding shear thinning and/or capable of suspending a high solidscontent for atomization. Optionally, pigments and/or aggregate materialcan be present in an amount capable of imparting an observable colorand/or texture. In one aspect, the alkaline oxide or alkaline hydroxideis an alkali earth metal or transition metal. In another aspect, thealkaline oxide or alkaline hydroxide excludes phosphoric acid orsparingly soluble inorganic phosphate salts, such as those that wouldprovide for a phosphate cement or ceramic. One or more of the componentsof the instant composition can be wet milled to a size of about 25 toabout 150 micron, about 50 to about 100 micron, or about 60 to about 80micron in average particle size to improve atomization and/or cure/setand/or appearance qualities of the coating.

The above atomizible spray coating can provide a thin, paint-likecoating for imparting hydrophobicity and/or fungal/bacterial resistanceto metallic and non-metallic surfaces and/or corrosion resistance tocorrodible metallic surfaces.

The rheology modifier/suspending agent can be at least one of guar gum,diutan gum, wclan gum, and xanthan gum. By using a rheologymodifier/suspending agent in an amount capable of providing shearthinning of either the acidic component or the basic component andfurther capable of suspending a high solids content of the basiccomponent for atomization, excellent paint-like coatings for impartingcorrosion resistance to metallic surfaces are obtained.

Examples of Group IV element with at least one carbon covalent bondinclude silanes, siloxanes, polysilanes, and polysiloxanes.(Poly)silanes and/or (p)olysiloxanes with reactive end-groups, e.g.alkoxy, as self crosslinking anionic or cationic emulsions or lowmolecular weight oligomers can be used, such as POLON™ silicone orpolysiloxane surfactants/sizings, DYNASYLAN™ functionalizedsilanes/siloxanes and poly- or oligomeric functionalized siloxanes, andthe like, in amounts of about 0.1 weight percent to about 20 weightpercent, or about 1 weight percent to about 10 weight percent.

In certain aspects of the present disclosure, the metallic surface isthat of a transition metal or its alloy, for example, iron, stainlesschromium, aluminum, copper, etc. Medical devices, components, equipment,

Water may be added to reduce the viscosity thereof, or other types ofviscosity reducing agents and/or rheology modifiers may be used.Commercial additives that prevent algae growth may also added to thisprecursor so that no algae growth occurs during storage of thisprecursor, however, due to the high pH of the formulation, it is notlikely such additives need to be added.

Experimental Section

The following examples are illustrative of the embodiments presentlydisclosed, and are not to be interpreted as limiting or restrictive. Allnumbers expressing quantities of ingredients, reaction conditions, andso forth used herein may be understood as being modified in allinstances by the term “about.” Accordingly, unless indicated to thecontrary, the numerical parameters set forth herein may beapproximations that may vary depending upon the desired propertiessought to be obtained. At the very least, and not as an attempt to limitthe application of the doctrine of equivalents to the scope of anyclaims in any application claiming priority to the present application,each numerical parameter should be construed in light of the number ofsignificant digits and ordinary rounding approaches. Severalexperimental examples, listed below, were conducted in order toformulate, coat, and demonstrate the attributes of the instantcompositions disclosed herein. pH values are provided using pH metershaving +/−0.5 accuracy.

The basic component includes, for example, basic oxides, hydroxides andbasic minerals. The basic component generally consists of a sparselysoluble oxide. In one aspect, a particle size less than 230 micron ofbasic component is used. The oxide may be represented by the formulaB^(2m)O_(m) or B(OH)_(2m), where B is a 2m-valent metal; and m is aninteger greater than 0. All divalent metal oxides (m=1), and sometrivalent metal oxides in reduced state fall into this category of smallsolubility product constant oxides. Examples of divalent oxides are, butnot limited to, magnesium oxide, barium oxide, zinc oxide, calciumoxide, and copper oxide. Examples of trivalent oxides in reduced stateare iron oxide (FeO), and manganese oxide (MnO).

In one aspect, a coating is prepared from about 30-50 weight percentsparingly soluble basic metal oxide/hydroxide, about 10 to about 50weight percent sparingly soluble inorganic silicate, and about 3 toabout 30 weight percent an acidic inorganic salt. In one exemplaryaspect, about 40 weight percent magnesium hydroxide, about 15-30 weightpercent calcium silicate (wollastonite) and about 3-15 weight percenttri potassium phosphate can be used. Applicants have observed thatwithout an effective amount of an aqueous soluble basic inorganic salt,e.g., K₃PO₄, the mixture of metal hydroxide and inorganic silicate isunstable after a short time after mixing with aqueous media. Forexample, the viscosity of the mixture of sparingly soluble basic metalhydroxide and sparingly soluble inorganic silicate goes up significantlywith time and cannot be sprayed, or stirred. It has been observed that aloading of soluble basic inorganic salt effective to stabilize themixture of metal hydroxide and inorganic silicate is about 3 weightpercent to about 30 weight percent when the basic organic salt istripotassium phosphate. While higher loadings of tripotassium phosphatecan be used, adjustment of the basic oxide/hydroxide is desirable toavoid slower set up. It has also been observed that a loading of solublealkali hydroxide effective to stabilize the mixture of sparingly solublemetal hydroxide and inorganic silicate is about 3 weight percent toabout 30 weight percent when the soluble basic organic salt istripotassium phosphate.

In another aspect, a coating is prepared from about 30-50 weight percentsparingly soluble basic metal oxide/hydroxide and about 10 to about 50weight percent inorganic silicate, and about 3 to about 30 weightpercent aqueous soluble basis inorganic salt. Other loadings may beused, for example, for coating horizontal surfaces.

Inorganic Coating Compositions

A range of compositions may be used as the hydrophobic and/orantifungal/antibacterial inhibitor and/or corrosion inhibiting coatingscommensurate with the spirit and scope of that disclosed and describedherein, the following exemplary, non-limiting example is provided:

Weight percent (%) Comments Sample A Magnesium Hydroxide (~40%)excellent long-term Wollastonite (~22%) storage stability; excellentPotassium Methyl Siliconate (~20%) resistant to wash-off; Xathum gum(~0.10%) excellent microbial remainder Water resistance; excellentcorrosion resistance Sample B magnesium hydroxide (~38-39%) excellentlong-term wollastonite (~20-21%) storage stability; excellent xanthiumgum (0.07%) resistant to wash-off; K₃PO₄ (~3.5%) excellent microbialPotassium Methyl siliconate (40% resistance; excellent solids) (~9%)corrosion resistance remainder water ~27-28% Sample C magnesiumhydroxide (~38-39%) excellent long-term wollastonite (~20-21%) storagestability; poor xanthium gum (0.07%) resistant to wash-off K₃PO₄ (~3.5%)remainder water ~27-28% Sample D Magnesium Hydroxide (~35%) poorlong-term storage Wollastonite (~19%) stability self-crosslinkinganionic siloxane emulsion (40% solids) (~10%) Xanthan gum (~0.10%)remainder Water Sample E Magnesium Hydroxide (~35%) excellent long-termWollastonite (~19%) storage stability; excellent silicon emulsionprocessing aid (~10%) resistant to wash-off; oligomeric or short-chainalkyl and/or excellent microbial phenyl siloxane with hydrolysableresistance; excellent alkoxy groups (~1%) corrosion resistance K₃PO₄(~4%) Xanthan gum (~0.10%) remainder Water Sample F Magnesium Hydroxide(~42%) excellent long-term Wollastonite (~22%) storage stability;excellent oligomeric or short-chain alkyl and/or resistant to wash-off;phenyl silane with hydrolysable alkoxy excellent microbial groups (~3%)resistance; excellent K₃PO₄ (~4%) corrosion resistance Xanthan gum(~0.10%) remainder Water Sample G Calcium Hydroxide (~35%) excellentlong-term Wollastonite (~22%) storage stability; excellent PotassiumMethyl Siliconatc (~20%) resistant to wash-off; Xathum gum (~0.10%)excellent microbial remainder Water resistance; excellent corrosionresistance Sample H Calcium hydroxide (~30-40%) excellent long-termwollastonite (~20-21%) storage stability; excellent xanthium gum (0.07%)resistant to wash-off; K₃PO₄ (~3.5%) excellent microbial PotassiumMethyl siliconate (40% resistance; excellent solids) (~9%) corrosionresistance remainder water ~27-28%

The above samples was prepared with soluble basic metal salt used atabout 0.01 to about 20 weight percent to that of the Mg(OH)₂.

The basic nature of the coating and/or monolith was determined byexposing the monolith to a fixed ratio of water/weight sample andmeasuring the pH. Conventional Ceramicrete and Grancrete materials wereused as controls. These control materials have significant amounts ofunreacted MgO, which can etch out of a a crushed or powder sample,forming MgOH. The test samples chosen form the similar binder MgKPO₄.Since the K_(sp) of the binder ceramic is MgKPO₄.6H₂O is 2.1×10⁻¹², thepresent samples having the basic alkali salt (e.g., K₃PO₄), which ishighly soluble in water, e.g., a solubility of about 90 g per 100 g ofwater, and an molar excess of the sparingly soluble basic metaloxide/hydroxide, the surface environment of the present samples isgreater than the Cermicrete and Grancrete samples.

The results of testing of a number of samples is provided in Table 1. Ascan be seen from Table 1, the present coatings and monoliths preparedtherefrom provided a basic environment of more than pH 10, and greaterpH (more basic) than conventional phosphate ceramics/cements, evenconventional phosphate ceramics/cements with silicate fillers, which arcprepared with essentially an excess of acidic phosphate precursor orwith equal molar amounts of acid/base components.

TABLE 1 pH of Samples and Controls Sample pH Comments DI water 6.62CONTROL - Molded Sample 6.70 Bulk sample was immersed in the Grancrete ©Sample water and pH of water measured after Weight Ratio (2:2:2) of ~1hr. (KH₂PO₄:MgO:Kaolin) CONTROL - Molded Sample 6.85 Bulk sample wasimmersed in the Grancrete © Sample water and pH of water measured afterWeight Ratio (2:2:2) of ~1 hr. (KH₂PO₄:MgO:Wollastonite) CONTROL -Molded Ceramicrete 7.72 Bulk sample was immersed in the (MgO/KH₂PO₄ +Wollastonite) water and pH of water measured after (Weight ratio =1:3:6) ~1 hr. CONTROL - Molded Ceramicrete 7.9 Bulk sample was immersedin the (Fly ash based), weight water and pH of water measured afterratio = MgO:KH₂PO₄:Fly ash = 1:3:6 ~1 hr. Sample A 9.43 Bulk sample(metal panel) was immersed in the water and pH of water measured after 1hr.

Water Uptake/Water Absorption Testing

For water absorption testing, an ASTM Cement substrate (thickness=˜0.5inch) was used as Control. Comparative sample and test samples ofcompositions A-D were prepared of 15-20 mils (1 mil=1/1000 inches)thickness. Weight gain of the control and each sample over the period oftime (one day, 2 days, and 8 days) after submerging in water. Weightgain was converted to weight per unit area (kg/m²). Results arerepresented as permeability (kg/m²).

Typically, a coating having a water permeability of about 0.3 kg/m² orless over 24 hours is classified as water impermeable. Samples absorbingwater or gaining weight less than 1 kg/m² are classified as hydrophobic(vapor permeable only). There is another classification whichclassifies.

As shown in Table 2, Water permeability of the cement control wasgreater than 5 kg/m². In comparison, samples A-D had water permeabilityof less than 1.0 kg/m². Sample A had a measured water permeability ofless than 0.2 kg/m² and less than 0.15 kg/m² or about 0.1 kg/m². Thus,the presently disclosed hydrophobic phosphate ceramic compositionsprovide water and permeability and/or improved water permeabilityresistance than conventional ceramic materials and/or coatings.

TABLE 2 Water absorption results for an exemplary embodiment Waterabsorption (Kg/m²) Sample (day 1; day 2; day 8) Comparative Example:5.58; 5.62; 5.93 Cement-Control Standard ASTM Cement Substrate Sample A0.10; 0.11; 0.11 (day 4)

Antifungal/Antimicrobial Testing

The purpose of the testing was to evaluate the surface of a treatedsample and untreated sample for antimicrobial effectiveness asdemonstrated by the JIS Z 2801:2010 test method. Sample A from Table 1was used for JIS Z 2801 testing. Each sample was tested in triplicate.Test pieces were approximately 50 mm×50 mm.

Procedure: Inoculum was prepared using Staphylococcus aureus ATCC#6538P, which was adjusted with a spectrophotometer to a concentrationof approximately 2.5-10×10⁸ Colony-Forming Units per milliliter(CFU/mL). Dilute nutrient broth prepared as described in the test methodwas used to further dilute the inoculum to 2.5-10×10⁵ CFU/mL. Theuntreated sample was tested in triplicate at Time=0 and Time=24 hours toestablish organism viability. The treated sample was tested at Time=24hours. Each sample piece was placed in sterile container and then wasinoculated with 0.4 mL of the inoculum. The inoculum was then coveredwith 40 mm² piece of sterile plastic (cut from sterile Whirlpak™ bags)in order to spread the inoculum evenly over the sample surface and holdit in place.

The samples were incubated for 24 hours at 35° C. and a relativehumidity of at least 90%. At the appropriate time, the samples wereplaced into a sterile Whirlpak™ bag and 10.0 mL of neutralizing brothwas added to the bag. The test pieces were thoroughly massaged in a bagcontaining the neutralizing broth (SCDLP) to facilitate the release ofthe inoculum from the sample surface into the neutralizing broth. Serialdilutions of the neutralizing broth containing the inoculum were plated.All plates were incubated at 35° C. for 24-48 hours. After incubation,bacterial colonies were counted and recorded.

Test Results are summarized in Table 3 below. An untreated MSL plasticcontrol recovered an appropriate amount of organism at Time=0 andTime=24 to confirm organism viability. The number of viable bacteria inthe test inoculum was 1.3×10⁵ CFU/mL. The number of viable bacteria inthe test inoculum was 5.9×10⁵ CFU/mL for Staphylococcus aureus and4.7×105 CFU/mL for Escherichia coli. This is the initial number ofbacteria placed onto to the sample surface for testing. This is theinitial number of bacteria placed onto to the sample surface fortesting. The value of the antimicrobial activity was calculatedaccording to the formula (I) listed below and recorded as log reduction.

R=(Ut−Uo)−(At−Uo)=Ut−At  (I)

Where, R: antimicrobial activity; Uo: average of logarithm numbers ofviable bacteria from untreated sample at Time=0; Ut: average oflogarithm numbers of viable bacteria from untreated sample at Time=24 h;and At: average of logarithm numbers of viable bacteria from treatedsample at Time=24 h.

TABLE 3 Staphylococcus aureus inhibition Testing of coatings disclosedherein Uo: Average of logarithm numbers of viable 4.02 bacteria fromuntreated control at Time = 0 U_(t): Average of logarithm numbers ofviable 4.60 bacteria from control sample at Time = 24 h A_(t): Averageof logarithm numbers of viable −0.0023 bacteria from Sample A at Time =24 h

According to the standard, an antibacterial product is determined tohave antibacterial effectiveness when the antibacterial activity (R) is2.0 or more. The sample coated with Sample A disclosed herein had an Rvalue of 4.60, indicating a percent reduction of viable bacteria of99.998 percent or excellent antibacterial activity against S. aureus.

Against Escherichia coli ATCC#8739, similar improvement was observed forthe instant coating prepared from the composition of Sample A. Thus, assummarized in Table 4,

TABLE 4 Escherichia coli inhibition Testing of coatings disclosed hereinUo: Average of logarithm numbers of viable 3.93 baeteria from untreatedcontrol at Time = 0 U_(t): Average of logarithm numbers of viablebacteria 5.23 from control sample at Time = 24 h A,: Average oflogarithm numbers of viable bacteria −0.20 froin BC I at Time - 24 hA_(t): Average .of logarithm numbers of viable bacteria 0.14 from ECH atTime = 24 h .1₁; Average of logarithm numbers of viable bacteria 3.84froM EC .at Time = 24 h

For comparison, a conventional phosphate ceramic sample (without a GroupIV-hydrocarbon bond component) was found to have an antibacterialactivity (R) of about 1.39 or a percent reduction of viable bacteria ofonly 95 percent.

Thus, the aforementioned compositions and coatings disclosed herein areeffective in inhibiting and preventing E. coli and otherhospital-related bacteria, as E. coli and other bacteria and/or fungusand are superior to existing compositions of silicate compositionwithout the Group IV-hydrocarbon bond component.

1-30. (canceled)
 31. A precursor composition, as an aqueous slurry orsuspension, the precursor composition comprising the presence of: atleast one sparingly soluble metal oxide/hydroxide having a solubilityconstant of 10⁻⁴ or smaller in aqueous media; at least one sparinglysoluble inorganic mineral having a solubility constant of 10⁻⁴ orsmaller in aqueous media; at least one soluble basic inorganic salthaving a solubility constant of 10⁻³ or greater in aqueous media; and atleast one hydrophobic agent, wherein the hydrophobic agent is of thegeneral formula (I) or (II) or (III):

where: R₁, R₂, R₃, and R₄ are, independently, hydrogen, C₁₋₂₀ alkyl,phenyl, aryl; where alkyl includes straight-chain, branched, cyclic oracylic alkyl, or haloalkyl; Y₁, Y₂, and Y₃ is, independently, hydroxyl,C₁₋₄ alkoxy, phenoxide, or halogen; or, Y₁, Y₂, and Y₃ is,independently, an alkali metal salt, an ammonium salt, an alkylammoniumsalt, a phenylammonium salt, or an alklyphenylammonium salt of Si—OH; bis 0-21; n is about 1,000 to about 1,000,000; and m is 0 to about 1,000;wherein the precursor composition is absent an acidic phosphateprecursor.
 32. The precursor composition of claim 31, wherein the atleast one sparingly soluble metal oxide/hydroxide is at least one ofmagnesium oxide or magnesium hydroxide.
 33. The precursor composition ofclaim 31, wherein the at least one sparingly soluble metaloxide/hydroxide is at least one of calcium oxide, calcium hydroxide,barium oxide, zinc oxide, copper oxide, or hydroxides thereof.
 34. Theprecursor composition of claim 31, wherein the at least one sparinglysoluble inorganic mineral is one or more of an inorganic mineralsilicate, wollastonite, talc, amorphous magnesium silicate, amorphouscalcium silicate, diatomaceous earth, aluminosilicate, olivine, calcinedkaolin, mullite, colloidal silica, silicon dioxide, or amorphous silicondioxide.
 35. The precursor composition of claim 31, wherein the at leastone soluble basic inorganic salt is one or more of an alkali metal oralkali earth metal salt of a phosphate or a silicate.
 36. The precursorcomposition of claim 31, wherein the at least one soluble basicinorganic salt is potassium phosphate salt (K₃PO₄).
 37. The precursorcomposition of claim 31, wherein the at least one soluble basicinorganic salt is potassium hydroxide.
 38. A method of preventing orreducing corrosion of a corrodible surface, the method comprising:contacting a corrodible surface with the combined composition of claim31; and preventing or reducing corrosion on the corrodible surface. 39.The method of claim 38, wherein the surface is metal or non-metal,associated with a medical article, medical device, medical equipment,hydroelectric dam, water treatment facility component, ship hull, or aphysical structure.
 40. The method of claim 38, wherein the surface,after contacting, provides a basic environment of at least pH 9 to pH14, the method further comprising preventing or reducing fungal orbacterial growth on the corrodible surface; or preventing or reducingattachment of Mollusca on the corrodible surface.
 41. The method ofclaim 40, wherein the Mollusca is a fresh water mussel, a zebra musselor quagga mussel.
 42. The method of claim 40, wherein the corrodiblesurface is associated with a water treatment facility.